Paper-like product and method of making the same.



LEO in BAEKELAND, or -YONKERS, NEW Yank, nsstenon 1'0 GENERAL BAxELIrE oomrnnx, on NEW YORK, N. Y., A CORPORATION on NEW YORK.

PAPER-111K111 rnonuor Ann Marne]: or MAKING- ran SAME.

Specification of Letters Patent.

Patented Nov. 16, 1915.,

No Drawing. Original application filed October 2, 1909, Serial No. 520,676. Divided and this application filed April 17, 1915. Serial No. 22,140.

To all whom it may concern:

Be it known .that I, LEO H. BAEKELANIl,

a citizen of the United States, residing at Yonkers, in the county of Westchester and State of New York, have invented certain new and useful Improvements in Paper- Like Products and Methods of -Making the Same, of which the following is a specification.

In my prior patents (see for example U. S. Patents Nos. 939,966,-November 16, 1909; 941,605, November 30, 1909; 942,699, December 7, 1909; and 942,808, December 7, 1909), and in my scientific and technical publications, (see Baekeland, March number, 1909, page 149, of the Journal of I trial and Engineering Chemistry, published by the American Chemical Society, Easton,

Pennsylvania; see also page 593 of the Tramsactz'ons of the American Electrochemical Society, Volume XV, 1909, published by the American Electrochemical Society, Lehigh University, South Bethlehem, Pa), I have described the manufacture of. many useful articles containing infusib-le condensation products of formaldehyde and phenols.

These substances work most advantageously in presence of fibrous bodies, either aloneor in conjunction with other fillers. Such mixtures have heretofore been made either in pasty or in powdered form, but their preparation and subsequent use involves several serious technical difiiculties. In the first case, where pasty mixturesare used, the material mixes with conslderable difficulty and does not allow rapid and accuthermore, the powdered mixture is rather bulky and rather difficult to introduce rap idly into molds of restricted size. In order to obviate this latter objection. it. is possible to compress the dry powdered mixture into sheets or masses of less bulk. But all these operations involve extra labor and considerable skill, and the success of proper molding depends very much on the way these preliminary treatments are carried out.

especially in hot the phenols and formaldehyde mixture or I have found a. simplification of considerable comn1ercial and technical value, which consists in preparing this mixture wet, so as to make a kind of paper, or cardboard, out of it, or any such bodies which may facilitate molding.

Instead of mixing and grinding the fibrous materials in a dry state with substances capable of yielding an infusible condensation product, I mix the fibrous materials in presence of water in suitable pro portions with such substances, the water being afterward eliminated from the mass by a process of drying. The wet mixing or grinding can be accomplished in a heater as practised in the art of paper-making, or in any other suitable device. For this purpose, wood pulp, ground pulp, sulfite pulp, soda pulp, cellulose, asbestos, rags, cotton, llnen, esparto grass, or in general, such fibrous materials as can be used for paper making, are finely divided and mixed in presence of Water in suitable proportions, and'with. the substances designated above, namely phenols and formaldehyde in proper proportion or their first reaction products,

products of same, either in liquid, in pasty or in solid form. or even a mixture of a phenolic body with formaldehyde. Any of these can be used with .or without the addition of suitable condensing agents. former case, I can use alkaline solutions of of the partial reaction pro-ducts of same, and the proportion of alkali used is not important or material, so long asany undesired excess thereof is eventually neutralized or eliminated by the addition of an acid or an acid salt ora suitable salt whi'chjby double decomposition eliminates the excess of alkali; Salts of aluminum, copper. iron,

zinc, nickel, cobalt. and in general such salts as produce insoluble hydroxids in presence of alkaline solutions ma be found to produce this effect." The additidn of these salts forltheelimination of excess of al-lcaline'con densing agent has the further advantage of modifying the color of the Product and of In the-- furnishing a Suitable filler and sizing. Any

"of the above mentioned partial reaction products of phenols and formaldehyde, and

. junction with thickening materials, as for instance. starch and gelatinous bodies, which tend to emulsify or suspend them better.

' and formaldehyde I mean to designate any product resulting from the direct or indition of these plastic mixtures and also for rect action of'a phenolic'body onformaldehyde. or equivalent 'methylene-containing substances, and which under the suitable action of heat and pressure, can be converted directly or indirectly into a final, hard, infusible condensation product of phenols and, formaldehyde.

M It is an advantageous feature of the present process that the beating in presence of water tends to eliminate from such partial reaction products any excess of uncombined phenols, the presence of which might be objectionable in the finished product.

By phenols, I desire to designate not only the first member of the phenol group, but

all its homologues or phenolic bodies or.

mixtures thereof, which can replace phenol or cresol .for this purpose. In my process, the formaldehyde can be replaced by its polymers or by such other substances as can, during the reaction, engender or replace formaldehyde.

The mixture can be varied so as to contain suitable filling materials, like china clay, soap stone, pulverized mica, aluminum powder, or in fact, any suitable inorganic or organic fillers which may be desirable as,

increasing the technical virtue or appearance of the finished products, or which may simplify the manufacture or commercial For 1nstance', a certain amount treatment. of pulverized final condensation product can be added. In the same way, colorin agents may be employed.

In some cases, it becomes desirable to add some sizing material, and for this purpose, any of the numerous sizing materials, which have been proposed, or which have been used, in paper-making, can be resorted to, as for instance starch,glue,.resinous soaps, etc. Very appropriate sizing materials whichcan be used in the preparageneral paper-making purposes, are the initial reaction products of phenols and formaldehyde themselves, or alkaline solutions thereof. As explained above, I may use an alkaline solution of partial condensation products, 0? again, I may use an alkaline solution, of the soluble, fusible condensation products of formaldehyde and phenols, described in my paper in the Journal of In- By partial reaction products of phenols dustm'al and Engineering Chemistry, (see August number, 1909, page 545 On Soluble, Fusible Resinous Condensation Products of Phenols and Formaldehyde) These alkaline solutions may be used alone or in conjunction with acids or suitable salts acting as condensing agents and added to the mass at any stage of the process of manufacture. The most convenient and quickest way for drying the mass is to convert it into paper or a paper-like body.

I wish it to be understood that under the name of paper I have designated here, not only the thin flexible variety of paper, but also any variety of cardboard or pulp-board of any desired thickness or shape, whether the same be formed directly in thick sheets, or whether these be obtained by superposition of several thinner sheets of paper as as 70% may in some cases be used, although the best proportions range from 15% to 50%. The mass, after going through the usual operations as practised in the art of paper-making, may be further submitted to any other treatment, as for instance, calendering; but in most cases, the paper prepared as above described can be used in its raw uncalendered state. This paper can be stored away indefinitely for future use; its ease of handling, freighting transporting, cutting and shaping, make it an unusually excellent starting point for molding and forming all kinds of articles. This not only reduces the cost of manufacture but renders the methods of operation more regular and certain. The process of molding is hereby reduced to its very simplest expression, relieving the manufacturer of molded articles of all other chemical or preliminary operations, and merely restricting his skill to relatively easy manufacturing methods, which mainly consist in hot pressing this paper can directly be pressed in hot button molds. In either case, the application of heat and 'pressure'not only gives shape to the articles, but transforms the lower con-' densation products of phenols and formaldehyde into the higher stages of condensation, which are infusible. The same proc special paper in suitable molds or devices.

ess can be followed for the manufacture of a continuous superficial layer, or in powderform, either during the .act of the manufacture of the paper, or any time afterward; or the molds or plates in which the paper is pressed, can be coated by dusting on, by sprinkling, or otherwise, these par- 'tial condensation products in powder form,

or by applying them in any other condition. Paper of different colors or of diflerent composition may be mixed or combined together in various Ways so as to obtain dur- 1 ing the act of hot pressing, numerous fancy articles or technical results, as marbleizing, tortoise shell efi'ects, mottling, etc. Molded objects can thus be made, which can stand water, cold or boiling, solvents and most chemicals. They are in this respect superior to rubber, celluloid, shellac compositions, and in fact all'plastics hitherto known.

My method can be carried out in the same Way when using asbestos fiber instead of organic fiber, or suitable mixtures of asbestos fiber and organic fiber can be compounded. All this according to the special uses for which the paper is intended. For certain purposes, as for instance electrical insulators, it becomes advantageous to use as much inorganlc material as possible to insure greater resistance to heat.

In certain cases where the pressed objects have to receive additional tensile strength, it is possible to introduce strengthening bodies, like metallic rods or wires, expanded metal, or tension members of any kind, and these can be embedded'before or after the act of molding.

, Instead of drying the mass in sheet form as practised in paper-making, I can dry it in bulk or in any form whatsoever, for instance, tubes or other suitable shapes.

This application is a division of my application erial No. 520,676, filed October 2 1909 I claim 1. The herein-described method of preparing a paper-like product, which consists in adding to wet paper pulp a phenolic condensation product in alkaline solution, and precipitating said condensation product on thefiber bya .process involving neutralization of the alkaline solvent.

. 2. The herein-described method of preparing a paper-like product, which consist in adding to wet paper pulp a phenolic condensation product in alkaline solution, said condensation product transformable by heat into an infusible body, and precipitating said condensation product on the fiber by a process involving neutralization of the alkaline solvent.

3. The herein-described method of preparing a paper-like product, which consists in adding to wet paper pulp a phenolic condensation product in alkaline solution, and precipitating the said condensation product on the fiber by means of a metal salt yielding an insoluble hydroxid by reaction with the alkali of the solvent.

4. The herein-described method of pre-' paring a paper-like product, which consists in adding to wet paper pulp a phenolic condensation product in alkaline solution, said condensation product transformable by heat into an infusible body, and precipitating the said condensation product on the fiber by means of a metal salt yielding an insoluble hydroxid by reaction with the alkali of the solvent.

5. In a method of preparing a paper-like product, the step which consists in adding to wet paper pulp a phenolic condensation product in state of solution.

6. In a method of preparing a paper-like product, the step which consists in adding to wet paper pulp a phenolic condensation product in state of solution, said condensation product tran'sformable by heat into an infusible body.

7. A paper-like product, comprising a fibrous material and a sizing, said sizing containing a phenolic condensation product precipitated upon the fiber.

8. A paper-like product, comprising a fibrous material and a sizing, said sizing 

